2.

3 Periodic Properties of Atoms

A valuable aspect of the arrangment of atoms on the basis of similar electronic configurations
within the periodic table is that an atom’s position provides information about its properties. Some
of these properties, and how they vary across periods and groups, are now discussed.
2.3.1 Ionization Energy
The ionization energy, also known as the ionization potential, is the energy required to
remove an electron from a gaseous atom or ion:
An+ (g)  A(n+1)+ (g) + e- ionization energy (IE) = ∆U
where n = 0 (first ionization energy), n = 1 (second ionization energy), and so on.
As would be expected from the effects of shielding, the ionization energy varies with
different nuclei and different numbers of electrons. Trends for the first ionization energies of the
early elements in the periodic table are shown in Figure 2.13. The general trend across a period
is an increase in ionization energy as the nuclear charge increases. However, the experimental
values show a break in the trend in the second period at boron and again at oxygen. Because boron
is the first atom to have an electron in a higher energy 2p orbital that is shielded somewhat by the
2s electrons, boron’s 2p electron is more easily lost than the 2s electrons of beryllium; boron has
the lower ionization energy.
(Gambar Konfigurasi Energy Be)
A t the fourth 2p electron, at oxygen, a similar decrease in ionization energy occurs. Here, the
fourth electron shares an orbital with one of the three previous 2p electrons
(Gambar atomic number)
(gambar spin), and the repulsion between the paired electrons (πc) reduces the energy necessary
to remove an electron from oxygen; oxygen has a lower ionization energy than nitrogen, which
has the 2p configuration.
Similar patterns appear in the other periods, for example Na through Ar and K through Kr,
omitting the transition metals. The transition metals have less dramatic differences in ionization
energies, with the effects of shielding and increasing nuclear charge more nearly in balance.
Much larger decreases in ionization energy occur at the start of each new period, because
the change to the next major quantum number requires that the new s electron have a much higher
energy. The maxima at the noble gases decrease with increasing Z , because the outer electrons
are farther from the nucleus in the heavier elements. Overall, the trends are toward higher
ionization energy from left to right in the periodic table (the major change) and lower ionization
energy from top to bottom (a minor change). The differences described in the previous paragraph
are superimposed on these more general changes.
2.3.2 Electron Affinity
Electron affinity can be defined as the energy required to remove an electron from a negative ion:
A- (g)  A (g) + e- electron affinity (EA) = ∆U
Because of the similarity of this reaction to the ionization for an atom, electron affinity is
sometimes described as the zeroth ionization energy . This reaction is endothermic (positive ∆U
) except for the noble gases and the alkaline earth elements. The pattern of electron affinities with
changing Z, shown in Figure 2.13, is similar to that of the ionization energies, but for one larger
Z value (one more electron for each species) and with much smaller absolute numbers. For either
of the reactions, removal of the first electron past a noble gas configuration is easy, so the noble
gases have the lowest electron affinities. The electron affinities are all much smaller than the
corresponding ionization energies, because electron removal from a negative ion (that features
more shielding of the nuclear charge) is easier than removal from a neutral atom.
Comparison of the ionization and electron affinity graphs in Figure 2.13 shows similar zigzag
patterns, but with the two graphs displaced by one element: for example, electron affinity shows a
peak at F and valley at Ne, and ionization energy a peak at Ne and valley at Na.
(Gambar number of electrons)
The patterns in these two quantities can more easily be seen by plotting energy against the number
of electrons in each reactant, as shown in Figure 2.14 for electron affinity and first and second
ionization energy.
The peaks and valleys match for all three graphs because the electron configurations match—for
example, there are peaks at 10 electrons and valleys at 11 electrons. At 10 electrons, all three
reactant species (F–, Ne, and Na+) have identical 1s2 2s2 2p6 configurations; these are by definition
isoelectronic species. The relatively high energy necessary to remove an electron from these
configurations is typical for configurations in which electron shells are complete. The next
electron, in an 11-electron configuration, is the first to occupy a higher energy 3s orbital and is
much more easily lost, providing a valley in each graph, corresponding to removal of an electron
from the 11-electron species Ne – , Na, and Mg + .
2.3.3 Covalent and Ionic Radii
The sizes of atoms and ions are also related to the ionization energies and electron affinities. As
the nuclear charge increases, the electrons are pulled in toward the c enter of the atom, and the size
of any particular orbital decreases. On the other hand, as the nuclear charge increases, more
electrons are added to the atom, and their mutual r epulsion keeps the outer orbitals large. The
interaction of these two effects, increasing nuclear charge and increasing number of electrons,
results in a gradual decrease in atomic size across each period. Table 2.8 gives nonpolar covalent
radii, based on bond distances in nonpolar m olecules. There are other measures of atomic size,
such as the van der Waals radius, in which collisions with other atoms are used to define the size.
It is difficult to obtain consistent data for any such measure, because the polarity, chemical
structure, and physical state of molecules change drastically from one compound to another. The
numbers shown here are sufficient for a general comparison of different elements.
There are similar challenges in determining the size of ions. Because the stable ions of the different
elements have different charges and different numbers of electrons, as well as different crystal
structures for their compounds, it is difficult to find a suitable set of numbers for comparison.
Earlier data were based on Pauling’s approach, in which the ratio of the radii of isoelectronic ions
was assumed to be equal to the ratio of their effective nuclear charges.
(Gambar tabel 2.8)
(Gambar tabel 2.9)
More recent calculations are based on a number of considerations, including electron density maps
from X-ray data that show larger cations and smaller anions than those previously found. Those in
Table 2.9 and Appendix B-1 were called “crystal radii” by Shannon 22 and are generally different
from the older values of “ionic radii” by +14 pm for cations and –14 pm for anions, as well as
being revised to accommodate more recent measurements. The radii in Table 2.9 and Appendix
B-1 can be used for rough estimation of the packing of ions in crystals and other calculations, as
long as the “fuzzy” nature of atoms and ions is kept in mind.
Factors that influence ionic size include the coordination number of the ion, the covalent character
of the bonding, distortions of regular crystal geometries, and delocalization of electrons (metallic
or semiconducting character , described in Chapter 7) . The radius of the anion is also influenced
by the size and charge of the cation. Conversely, the anion exerts a smaller influence on the radius
of the cation. The table in Appendix B-1 shows the effect of coordination number.
The values in Table 2.10 show that anions are generally larger than cations with similar numbers
of electrons. The radius decreases as nuclear charge increases for ions with the same electronic
structure, with the charge on cations having a strong effect, for example in the series Na+, Mg2+,
Al3+ . Within a group, the ionic radius increases as Z increases because of the larger number of
electrons in the ions and, for the same element, the radius decreases with increasing charge on the
cation. Examples of these trends are shown in Tables 2.10, 2.11, and 2.12.
(Gambar tabel 2.10)
(Gambar tabel 2.11)
(Gambar tabel 2.12)
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2.3 Sifat Periodik Atom
Aspek penting dari pengaturan atom berdasarkan konfigurasi elektron serupa dalam tabel periodik
yaitu bahwa posisi atom memberikan informasi tentang sifat-sifatnya. Beberapa sifatnyaini, dan
bagaimana mereka bervariasi di seluruh periode dan kelompok, sekarang akan dibahas.
2.3.1 Energi Ionisasi
Energi ionisasi (potensi ionisasi) adalah energi yang dibutuhkan untuk mengeluarkan elektron dari
atom atau ion gas:
An+ (g)  A(n+1)+ (g) + e- energi ionisasi (IE) = ∆U
di mana n = 0 (energi ionisasi pertama), n = 1 (energi ionisasi kedua), dan seterusnya.
Seperti yang diharapkan dari efek shielding, energi ionisasi bervariasi dengan inti dan jumlah
elektron yang berbeda. Untuk energi ionisasi pertama dari unsur-unsur awal dalam tabel periodik
ditunjukkan pada Gambar 2.13.
(Gambar 2.13)
Kecenderungan umum di bagian periode adalah peningkatan energi ionisasi. Namun, nilai-nilai
eksperimen menunjukkan pemutusan pada periode kedua pada boron dan oksigen. Hal tersebut
tejadi karena boron adalah atom pertama yang memiliki elektron dalam energi tertinggi pada
orbital 2p yang terlindungi oleh elektron pada orbital 2s, elektron 2p pada Boron lebih mudah
hilang daripada elektron 2s pada Berilium; Boron memiliki energi ionisasi yang lebih rendah.
(Gambar Konfigurasi Energi Be)
Pada elektron 2p keempat, pada oksigen, terjadi penurunan serupa dalam energi ionisasi. Di sini,
elektron keempat berbagi orbital dengan salah satu dari tiga elektron 2p sebelumnya (gambar spin)
dan tolakan antara elektron berpasangan (πc) mengurangi energi yang diperlukan untuk
mengeluarkan elektron dari oksigen sehingga oksigen memiliki energi ionisasi yang lebih rendah
daripada nitrogen (yang memiliki konfigurasi 2p)
Pola serupa juga muncul pada periode lain, misalnya Na melalui Ar dan K melalui Kr, dalam
menghilangkan logam transisi. Logam transisi memiliki perbedaan yang kurang menggemparkan
dalam energi ionisasi, dengan efek shielding dan peningkatan muatan yang mengandung atom
yang hampir seimbang.
Penurunan energi ionisasi yang jauh lebih besar terjadi pada awal setiap periode baru, karena
perubahan ke nomor kuantum utama berikutnya mensyaratkan bahwa elektron baru memiliki
energi yang jauh lebih tinggi. Maksimum di gas mulia menurun dengan meningkatnya Z, karena
elektron terluar (yang jauh dari inti) dalam unsur-unsur yang lebih berat. Secara keseluruhan, tren
menuju energi ionisasi yang lebih tinggi dari kiri ke kanan dalam tabel periodik (perubahan besar)
dan energi ionisasi yang lebih rendah dari atas ke bawah (perubahan kecil). Perbedaan yang
dijelaskan dalam paragraf sebelumnya ditumpangkan pada perubahan yang lebih umum ini.